Process for manufacture of alcohols

ABSTRACT

PROCESS FOR THE MANUFACTURE FROM SATURATED ALIPHATIC OR ALICYCLIC HYDROCARBONS OF CORRESPONDING ALCOHOLS BY THE LIQUID PHASE OXIDATION METHOD WITH THE USE OF MOLECULAR OXYGEN-CONTAINING GAS, CHARACTERIZED IN THAT THE OXIDATION IS CARRIED OUT IN THE PRESENCE OF A CATALYST SELECTED FROM THE GROUP CONSISTING BORIC ACIDS, BORIC ACID ANHYDRIDE AND MIXTURES THEREOF, AND A PROMOTER SELECTED FROM AMMONIA, AMMONIACAL BASIC COMPOUNDS, AND COMPOUNDS WHICH GENERATE AMMONIA OR HEATING.

United States Patent Oficc Patented May 2, 1972 U.S. Cl. 260-617 H 4 Claims ABSTRACT OF THE DISCLOSURE Process for the manufacture from saturated aliphatic or alicyclic hydrocarbons of corresponding alcohols by the liquid phase oxidation method with the use of molecular oxygen-containing gas, characterized in that the oxidation is carried out in the presence of a catalyst selected from the group consisting of boric acids, boric acid anhydride and mixtures thereof, and a promoter selected from ammonia, ammoniacal basic compounds, and compounds which generate ammonia on heating.

This application is a continuation-in-part of U.S. application Ser. No. 595,606, filed Nov. 21, 1966 and now abandoned.

The present invention relates to a process for the manufacture of the corresponding alcohols from aliphatic or alicyclic hydrocarbons by oxidizing the same by a liquid phase oxidation method with the use of a molecular oxygen-containing gas; more particularly the present invention relates to a method of elevating the yield of the resulting alcohols by carrying out the said oxidation in the presence of a catalyst chosen from the group consisting of boric acids, boric acid anhydride and mixtures of these and promoters chosen from the group consisting of ammonia, ammoniacal basic compounds, and compounds which liberate ammonia on heating.

iHeretofore, it has been well known to produce alcohols from aliphatic or alicyclic hydrocarbons by the liquid phase oxidation method by which the oxidation is carried out in the presence of boric acid with the use of molecular oxygen containing gas. According to this method, the boric acid is present in the liquid phase in the form of suspension, the same stabilizing the resulting alcohol by converting it into its boric acid ester. As a result, it prevents the gradual oxidation of the resulting alcohol. Boric acid, however, is dehydrated at a reaction temperature in the vicinity of 150 to 180 C. to give partially dehydrated products such as meta-boric acid and pyro-boric acid. Simultaneously, a clogging phenomenon occurs, with material being deposited on the wall or precipitated, the same being unable to exist in the state of a suspension. Needless to say, the outcome of the above is that an even distribution of boric acid in the hydrocarbon is prevented, that the esterification reaction of the resulting alcohol and boric acid is prevented, and therefore that the yield of the alcohol is lowered. Furthermore, when the process is practiced industrially, this clogging phenomenon constitutes an obstacle in the operation of the plant.

Various attempts have been made to avoid this clogging phenomenon. For instance, in Belgian Pats. Nos. 652,628 and 658,308, and French Pat. No. 1,384,586, a method is attempted comprising dehydrating boric acid to meta-boric acid in hydrocarbons in advance, feeding the mixture into a reactor and oxidizing the hydrocarbons by introducing oxygen and heating. French Pat. No. 1,379,783 discloses a method of improving the state of dispersion by means of a forcible mechanical stirring. However, none of these methods has given any substantial solution of the problem of the clogging phenomenon, and in order to make the method feasible on an industrial basis, a surer method of solution has been desired.

Russian Pat. No. 106,9 14, French Pats. Nos. 1,379,747 and 11,379,783 disclose a method involving the use of boric acid anhydride as a catalyst. By such a process, with the pure anhydride, instead of the absence of the clogging phenomenon, the reaction hardly proceeds. However, when the process is carried out with the use of a commercially available boric acid anhydride, it is found that the reaction proceeds but with attendant clogging phenomenon. The purity of the commercial grade boric acid anhydride as percentage of B 0 is found to be 86.5%, and the boric acid anhydride contains a great quantity of meta-boric acid formed by moisture absorption. It is clear from the above that the, clogging phenomenon can be prevented if a pure boric acid anhydride is used, but the intended oxidation reaction cannot be made to proceed sutliciently; therefore, such method cannot be utilized in industrial production.

Accordingly, it has long been the desire of the industry to provide an improved process eliminating the above noted disadvantages. This has now been accomplished in accordance with the present invention, comprising an improved process characterized by the use of a catalyst selected from boric acids, boric acid anhydride and mixtures thereof and a promoter selected from ammonia, ammoniacal basic compounds, and compounds which libcrate ammonia on heating.

Accordingly, an object of the present invention is to provide an improved process for the manufacture of the corresponding alcohols at a high yield by oxidizing aliphatic or alicyclic hydrocarbons by a liquid phase oxidation method with the use of a molecular oxygen-containing gas.

Another object of the present invention is to provide a method of preventing the clogging of the catalyst in the liquid phase in the said liquid phase oxidation method, and making the oxidation reaction proceed rapidly by maintaining the catalyst completely in a suspended state.

It is also an object of the present invention to manufacture the intended alcohols at a low cost by preventing the precipitation of the catalyst on the bottom of a reaction apparatus or the deposition thereof on the wall of the apparatus or the choking of pipes caused by the clogging phenomenon, and omitting ordecreasing the equipment needed for the prevention or removal of these phenomena.

It is yet a further object of the present invention to provide such an improved process characterized by the use of a catalyst selected from boric acids, boric acid anhydride and mixtures thereof and a promoter selected from ammonia, ammoniacal basic compounds, and compounds which liberate ammonia on heating.

IThBSC and other objects will be made more apparent from the description which follows.

As a result of extensive researches with the above objects in mind, it has been found in accordance with the present invention that if the oxidation reaction is carried out in the presence of a catalyst chosen from the group consisting of boric acids, boric acid anhydride and mixtures of these and promoters chosen from the group consisting of ammonia, ammoniacal basic compounds and compounds which liberate ammonia on heating when alcohols are manufactured from aliphatic or alicyclic hydrocarbons by the liquid phase oxidation method with the use of molecular-oxygen-containing gas, it is possible to maintain the catalyst completely in the suspended state in the liquid phase, to make the oxidation of the hydrocarbons to the corresponding alcohols proceed'rapidly, and thus to greatly elevate the yield of the intended alcohols.

Heating of ortho-boric acid (H BO gives various partially dehydrated products, as well as the completely dehydrated boric 'acid anhydride (B As the partially dehydrated products, mesoboric acid (H B 0 metaboric acid (H B O hexahydrotetraboric acid (H B O dihydrotetraboric acid (H B O hexahydrohexaboric acid (H B O dihydrohexaboric acid (H B O hexahydrooctoboric acid (H B O dihydrooctoboric acid (H B O dihydrodecaboric acid (H B O dihydrododecaboric acid (H B O etc., are known. Orthoboric acid and each of the above single compounds produced by its dehydration are referred generically to boric acids in this specification. As is clear from calculation, the B 01 content of each of these boric acids, is in the above order, 56.4%, 66.0%, 79.5%, 72.2%, 88.4%, 79.5%, 92.1%, 83.7%, 93.9%, 95.0% and 96.0%. Of course, there are other partially dehydrated products whose B 0 content shows other value, but they are considered to be mixtures of the above boric acids and boric acid anhydride in various proportions. Therefore, by the catalyst chosen from the group consisting of boric acids, boric acid anhydride and mixtures of these are meant orthoboric acid and all of its dehydrated compositions, that is, the compositions having a B O content in the range of 56.4 to 100%. Hereinafter, these dehydrated compositions shall be called dehydrated boric acid.

In the development of the present invention, the relationship among the B 0 content of dehydrated boric acid, the occurrence of clogging and the progress of oxidation reaction was studied. Parafiins were oxidized in a liquid phase by using as a catalyst dehydrated boric acid prepared by heating and dehydrating orthoboric acid under reduced pressure to various extents, the results obtained being shown in Table 1. This liquid phase oxidation was carried out by putting 100 g. of a mixture of n-par'affins having 12, 13, and 14 carbon atoms with an average molecular weight of 185 into a glass cylindrical reaction vessel, adding 2.8 g. of the dehydrated boric acid, blowing a mixed gas having an oxygen concentration of 5% and a nitrogen concentration of 95% at a rate of one litre 'per ninute, and reacting them at 170 C. for 3 hours. Table 1 shows dehydrated boric acid in terms of percent of B 0 content. As is clear from the above, the composition with 88.4% B 0 content is dihydrotetraboric acid (H EgO-Q and others are considered to be mixtures of various boric acids. In the table, the symbol shows that the clogging or reaction occurred, and the symbol shows that it did not.

TABLE 1 B 03 percent Clogging Reaction llll++++ Extensive research was therefore made in an attempt to find a method by which it is possible to make the reaction proceed by using a dehydrated boric acid with small water content (less than 10%) which did not cause clogging in the above test. In consequence, it was discovered that a very small amount of an ammonia base, if present in the reaction system, functions as a promoter, and makes the reaction proceed very rapidly. Surprisingly enough, subsequent studies showed that if such a promoter is used, the reaction proceeds smoothly even in the presence as a catalyst of a dehydrated boric acid with a relatively large water content which brought about clogging in the previous tests. It was further discovered that such promoters can be chosen widely from the group consisting of ammonia, ammoniacal basic compounds and compounds which liberate ammonia on heating.

The aliphatic or alicyclic hydrocarbons usable as the starting material in this invention are cyclic paraffins, isoparafiins, n-paraffins having at least 3 carbon atoms, and mixtures of these, and preferably parafiins having at least 6 carbon atoms. According to the present invention, the corresponding alcohols predominantly comprising secondary alcohols can be obtained from these paraffins.

If the hot dehydration reaction of orthoboric acid is carried out under normal atmospheric pressure, dehydrated boric acid is obtained as a glass melt. On the other hand, if it is carried out under reduced pressure, a dehydrated powdery substance is obtained. As the catalyst to be used for the liquid phase oxidation method of this invention, the powdery substance is suitable.

Usuable as the promoters according to this invention are such materials as ammonia, ammoniacal basic compounds such as ammonium carbonate and ammonium acetate, and compounds which liberate ammonia on heating, such as urea and thio-urea; amines, for instance, mono-, diand tri-alkyl amines such as methylamine, ethylamine, propylamine, isopropylamine, butylamine, secbutylamine, tert-butylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, trimethylamine, triethylamine, tripropylamine, and triisopropylamine, alkylene amines and diamines such as allylamine, ethylene diamine, propylene diamine, and hexamethylene diamine, mono-, diand tri-alkanol amines such as ethanolamine, pro panolamine, isopropanolamine, butanolamine, diethanolamine, dipropanolamine, diisopropanolamine, triethanolamine, triisopropanolamine and choline; amides such as formamide, acetamide, acetomethylamide, diacetamide and benzamide, hydrazines such as hydrazine, monoand dialkyl hydrazine, e.g., methylhydrazine, ethylhydrazine, propylhydrazine, dimethylhydrazine and phenylhydrazine, hydrazides such as acetohydrazide and sym-diacetylhydrazide, amino acids such as glycine, alanine and anthranilic acid, nitrogen-containing heterocyclic bases, for instance, imides such as succinimide, maleicimide and phthalimide, imines such as ethylene imine, propylene imine and hexamethylene imine, pyridines, such as pyridine, picoline, lutidine and ethylpyridine, piperizines, pyrazines, piperazines, pyrimidines, tetrazines, pyrroles, triazoles, tetrazoles, indoles, carbazoles, and quinolines.

The amount of such promoters to be used is not limited but such promoter is preferably employed in an amount of 0.0001 to 1 mole per mole of catalyst. Particularly, the amount of 0.001 to 0.1 mole per mole of catalyst gives desirable results.

These promoters are fed to the reaction system either continuously or intermittently by any of the preferable methods of dissolving or suspending them in the starting hydrocarbons, mixing them with the catalyst, making them absorb on the catalyst or making them present in a blowing gas.

The process of this invention can be practiced either batch-wise, semi-batchwise or continuously. In the practice of the process of this invention, those conditions usually adopted in the liquid phase oxidation method for hydrocarbons can be generally used. Specifically, the

amount of the catalyst to be used is 0.01 to 10 moles per mole of the starting hydrocarbons, with the amount of 0.05 to 0.25 mole in particular giving good results. The concentration of oxygen in the blowing gas can be varied over a wide range, but the amount of 3-10% gives good results. The amount of the blowing gas relates somewhat to the form of the reaction apparatus, but the amount in a volumetric ratio of l-100, especially 5-50, to 1 (starting material) per minute is preferable. The reaction temperature is 100 to 250 C., and the temperature in the range of 130-200 C. gives especially desirable results. The reaction can be carried out either at atmospheric pressure or at elevated pressure. The pressure is properly selected in consideration of the boiling point of the hydrocarbons, the reaction temperature and the partial pressure of oxygen. If necessary, it is possible to carry out the reaction by the conjoint use of an anti-oxidizing solvent, for instance, ether, with the hydrocarbons.

In the following pages, the invention will be explained in detail with reference to examples.

The conversion and the selectivity in the examples are the values measured in accordance with the following definitions.

(Mole of the resulting alcohol) (Mole of the consumed hydrocarbons) EXAMPLE I One hundred grams of a mixture of n-parafiins having 12, 13, and 14 carbon atoms and an average molecular weight of 185 were put into a glass cylindrical reaction vessel, followed by addition of 2.8 g. of a dehydrated boric acid with a B content of 98.5%. A gaseous mixture comprising 5% of oxygen and 95% of nitrogen was blown thereinto at a rate of one litre per minute, together with ammonia gas at a rate of 0.2 cc. per minute, and the reaction was carried out for 2.5 hours at 175 C. At the completion of the reaction, the reacted liquor was hydrolyzed with hot water. The resulting oily layer containing the sec-alcohols with the corresponding carbon number was then subjected to chemical analysis and gas-chromatograph analysis. The results are as follows:

Hydroxyl value 70.0 Acid value 4.2 Ester value 11.7 Conversion (percent) 31.0 Selectivity (percent) 72.0

When ammonia was not present in the blowing gas, the reaction hardly proceeded.

EXAMPLE II Hydroxyl value 66.5

Acid value 3.0

Ester value 7.9

Conversion (percent) 25.6

Selectivity (percent) 71.1 EXAMPLE III Two hundred cubic centimeters of diphenyl ether, 40 g. of propane and 3 g. of a dehydrated boric acid with a B 0 content of 98.5% were put into a stainless steel autoclave equipped with a reflux condenser cooled to -50 C. While stirring, the temperature was raised to 170 C. At the reaction pressure of about 30 k-g/cmfi, a gaseous mixture comprising 5% of oxygen and of nitrogen containing p.p.m. of ammonia gas was blown thereinto at a rate of one litre per minute, and the reaction waseffected for 2 hours. The reacted liquor was treated with hot water. Isopropyl alcohol was mainly produced.

EXAMPLE IV One hundred grams of a mixture of n-paraffins with 12, 13, and 14 carbon atoms and an average molecular weight of 185 were put into a glass cylindrical reaction vessel, followed by addition of 4.2 g. of a dehydrated boric acid with a B 0 content of 98.5%. A gaseous mixture comprising 5% of oxygen and 95% of nitrogen was blown thereinto at a rate of one litre per minute together with about 0.1 cc. per minute of ammonia gas, and the reaction was etfected for 2.5 hours at 175 C. The reacted liquor was hydrolyzed and analyzed. The results are as follows:

Hydroxyl value 47.1

Acid value I 2.0

Ester value 4.0

Conversion (percent) 18.0

Selectivity (percent) 82.1 EXAMPLE V One hundred grams of cyclododecane were put into a glass cylindrical reaction vessel, followed by addition of 4.0 g. of a dehydrated boric acid with a B 0 content of 98.5%. A gaseous mixture comprising 5% of oxygen and 95% of nitrogen was then blown at a rate of one litre per minute together with about 0.1 cc. of ammonia gas per minute, and the reaction was carried out at C. for 2.5 hours.;The results of analysis are as follows:

. Percent Conversion 19.5 Selectivity 83.5

EXAMPLE VI Two hundred grams of cyclohexane and 10.0 g. of a dehydrated boric acid with a B 0 content of 98.5% were put into a stainless steel autoclave. While stirring, a gaseous mixture comprising 5% of oxygen and 95% of nitrogen containing about 100 p.p.m. of ammonia gas was blown thereinto at a rate of two litres per minute, and the reaction was effected for 2 hours at a temperature of 170 C. and a pressure of 10 kg./cm. The results of analysis are as follows:

Percent Conversion 14.5

Selectivity 88.5

EXAMPLE VII hydrolyzed and analyzed as follows:

Hydroxyl value 69.8 Acid value 3.2 Ester value 8.5 Conversion (percent) 26.7 Selectivity (percent) 75.0

EXAMPLE VIII The procedure of Example VII was repeated except that 0.005 mole of succinicimide was added at an early stage of reaction. The reacted liquor was: hydrolyzed and analyzed. The results are as follows:

EXAMPLES XIV-XXII Hydroxyl value 485 The procedure of ExampleVII was repeated except Add Value 21 that each of the compounds indicated in Table II was Ester value 5.1 added at all e rly stage of reaction. The reacted liquor conveys-H 135 was hydrolyzed and analyzed. The results are shown in Select1v1ty (percent) 80.5 Table 2.

. TABLE 2 Conv rl Amount Hydroxyl Acid Ester 510%, 0 Example Compound (mole) value value value percent percent;

14 Diethylamine 0.00015 58.0 3. 0 6,2 15 Ethylene imine 0.002 51. 7 2.9 6.0 10--. Formamide 0. 001 50.9 3.2 5.9 23.9 750 17 Hydrazine'. 0. 001 58.3 2.8 5.7 24.5 75's 18 Acetohydrazide 0. 002 57.9 2.7 0.3 24.1 78 5 19. lyeine 0. 002 56.8 2.7 as 22.0 78 8 yrol 0.002 67.2 3.0 7.1 22.0 77's 21 Tetrazol. 0. 001 69.4 3. 3 7.0 23 7 22 dol 2 56.5 2.6 6.5 225 1 EXAMPLE IX The procedure of Example VII was repeated except that 0.002 mole'of pyridine was added at an early stage of reaction. The reacted liquor was hydrolyzed and analyzed. The results are as follows:

Hydroxyl value 56.6

Acid value 2.9

Ester value 6.1

Conversion (percent) 22.0

Selectivity (percent) 76.5

EXAMPLE X The procedure of Example VII was repeated except that 0.002 mole of ammonium acetone was added at an early stage of reaction. The reacted liquor was hydrolyzed and analyzed. The results are as follows: I

Hydroxyl value 59.0 Acid value 3.3 Ester value 8.3 Conversion (percent) 23.5 Selectivity (percent) 75.5

EXAMPLE XI The procedure of Example VII was repeated except that 0.001 mole of ammonium carbonate was added at an early stage of reaction. The reacted liquor was hydrolyzed and analyzed. The results are as follows:

Hydroxyl value 68.5

Acid value 2.9

Ester value 6.8

Conversion (percent) 26.0

Selectivity (percent) 76.5 EXAMPLE XII The procedure of Example VII was repeated except that 0.002 mole of methylamine was added at an early stage of reaction. The reacted liquor was hydrolyzed and analyzed. The results are shown as follows:

Hydroxyl value 57.2 Acid value 3.1 Ester value 6.3 Conversion (percent) 24.1 Selectivity (percent) 75.1

EXAMPLE XIII The procedure of "Example VII was repeatedexcept that 0.002 mole of monoethanol amine was added at an early stage of reaction. The reacted liquor was hydrolyzed and analyzed. The results are as follows:

Hydroxyl value 58.4 Acid value 3.0 Ester value 7.4 Conversion (percent) 23.9

Selectivity (percent) 75.5

EXAMPLE XXIII One hundred grams of a mixture of n-parafiins with 12, 13, and 14 carbon atoms and an average molecular weight of 185 were put into a glass cylindrical reaction vessel, followed by addition of 5.0 g. of orthoboric acid. A gas- When the blowing gas was accompanied by about 0.2 cc./min. of ammonia gas, the following results were obtained:

40 Hydroxyl value 60.0 Acid value 2.8 Ester value 6.5 Conversion (percent) 23.5 Selectivity (percent) 74.6

EXAMPLE One hundred grams of a mixture of n-paraifins with 12, 13 and 14 carbon atoms and an average molecular weight of 185 were put into a glass cylindrical reaction vessel, followed by addition of 4 g. of metaboric acid. A gaseous mixture of 5% of oxygen and 95% of nitrogen was blown thereinto at a rate of one litre per minute, and the reaction was effected for 2.5 hgurs at 175 C. The reacted liquor was hydrolyzed and analyzed. The results are as follows:

Hydroxyl value 35.2 Acid value 2.0 Ester value 5.2 Conversion (percent) 15.1 Selectivity (percent) 78.0

When the blowing gas was accompanied by 100 p.p.m. of ammonia gas, the following results were obtained:

Hydroxyl value 60.0 Acid value 2.8 Ester value 6.5 Conversion (percent) 23.5 Selectivity (percent) 74.6

EXAMPLES XXV XXXVI The procedure of Example VII was repeated except that each of the compounds indicated in Table 3 was added at an early stage of reaction. The resulting liquor r was hydrolyzed and analyzed. The results are shown in Table 3.

TABLE 3 Conver- Selec- Amount Hydroxyl Acid Ester sion, tlvity Example Compound (mole) value value value percent percent,

25--- O. 1 33. 4 2. 7 14. 2 14. 1 75. 2 26 0. 002 57. 5 3. 2 5. 2 25. 74. 1 27. 0. 002 56. 8 3. 4 5. 3 24. 5 75. 2 28 Allylamine 0. 002 57. 3 2. 8 5. 6 24. 3 75. 0 29.-. Hexamethylene diami 0-. 0. 001 67. 5 3.4 7. 5 26. 3 74. 5 30.-- Triethanolamlne 0. 002 57. 3 2. 8 6. 7 23. 7 74. 7 '21 Dianetanaide O. 002 57. 1 3. 1 5. 7 23. 7 75. 6 32.-. Phenylhydrazlne 0. 001 56. 3 2. 4 6. 3 22. 1 79. 2 33-.. Anthranilic acid 0. 002 55. 2 3 5. 9 21. 8 79. 1 34.-- Piperidine 0. 002 58. 1 3. 0 5. 8 24. 0 76. 1 35.-- Pycoline O. 002 56. 3 2. 9 5. 8 22. 2 76. 7 36 Quinoline 0. 002 59. 1 3. 2 8. 2 23. 5 76. 0

What 1s claimed 1s: (x111) amino acids selected from glycine, alanine and 1. In a process for the production of the corresponding alcohols from cyclic paraffins, isoparaflins and n-paraflins having at least three carbon atoms by oxidizing said cyclic paraffins, isoparaffins and n-parafiins with a molecular oxygen-containing gas in the liquid phase in the presence of a catalyst selected from the group consisting of boric acids, boric acid anhydride and mixtures thereof and hydrolyzing the resulting borate ester to form said corresponding alcohols, the improvement which comprises carrying out said oxidizing in the presence of a promoter, in an amount of 0.0001-1 mol per one mol of said catalyst, selected from the group consisting of (i) ammonia,

(ii) ammonium salts selected from ammonium acetate and ammonium carbonate,

(iii) urea,

(iv) mono-, diand trialkyl monoamines,

(v) alkylene diamines,

(vi) mono-, diand trialkanol amines,

(vii) amides selected from formamide, acetamide,

acetomethylamide, diacetamide and benzamide,

(viii) imides selected from succinimide, maleicimide and phthalimide,

(ix) hydrazine,

(x) monoand dialkyl hydrazine,

(xi) phenyl hydrazine,

(xii) hydrazides selected from acetohydrazide and symdiacetylhydrazide,

anthranilic acid,

(xiv) pyridines selected from pyridine and picoline,

(xv) quinoline,

(xvi) pyrrole,

(xvii) tetrazole, and

(xviii) indole.

2. The process of claim 1 wherein said catalyst has a B 0 content of at least 3. The process of claim of claim 1 wherein said promoter is employed in an amount 0.001-0.l mol per one mol of said catalyst.

4. The process of claim 1 wherein ammonia gas is used as said promoter.

References Cited UNITED STATES PATENTS 3,301,887 1/1967 Kirshenbaum et 'al. 260462 A 2,721,181 10/1955 Lawrence et a1. 2606l7 HX 2,962,361 11/1960 Spiller et al 23260 OTHER REFERENCES Lowry, Inorg. Chem., MacMillan & (20., London, 1931, pp. 700, 701, and 703.

HOWARD T. MA RS, Primary Examiner US. Cl. X.R. 260462 A, 631 B, 639 B 

